Toward large-scale, ordered and tunable Majorana-zero-modes lattice on iron-based superconductors.

Majorana excitations are the quasiparticle analog of Majorana fermions in solid materials. Typical examples are the Majorana zero modes (MZMs) and the dispersing Majorana modes. When probed by scanning tunneling spectroscopy, the former manifest as a pronounced conductance peak locating precisely at zero-energy, while the latter behaves as constant or slowly varying density of states. The MZMs obey non-abelian statistics and are believed to be building blocks for topological quantum computing, which is highly immune to the environmental noise. Existing MZM platforms include hybrid structures such as topological insulator, semiconducting nanowire or 1D atomic chains on top of a conventional superconductor, and single materials such as the iron-based superconductors (IBSs) and 4Hb-TaS2. Very recently, ordered and tunable MZM lattice has also been realized in IBS LiFeAs, providing a scalable and applicable platform for future topological quantum computation. In this review, we present an overview of the recent local probe studies on MZMs. Classified by the material platforms, we start with the MZMs in the iron-chalcogenide superconductors where FeTe0.55Se0.45and (Li0.84Fe0.16)OHFeSe will be discussed. We then review the Majorana research in the iron-pnictide superconductors as well as other platforms beyond the IBSs. We further review recent works on ordered and tunable MZM lattice, showing that strain is a feasible tool to tune the topological superconductivity. Finally, we give our summary and perspective on future Majorana research.

Nanoscale Manipulation of Wrinkle-Pinned Vortices in Iron-Based Superconductors.

The controlled manipulation of Abrikosov vortices is essential for both fundamental science and logical applications. However, achieving nanoscale manipulation of vortices while simultaneously measuring the local density of states within them remains challenging. Here, we demonstrate the manipulation of Abrikosov vortices by moving the pinning center, namely one-dimensional wrinkles, on the terminal layers of Fe(Te,Se) and LiFeAs, by utilizing low-temperature scanning tunneling microscopy/spectroscopy (STM/S). The wrinkles trap the Abrikosov vortices induced by the external magnetic field. In some of the wrinkle-pinned vortices, robust zero-bias conductance peaks are observed. We tailor the wrinkle into short pieces and manipulate the wrinkles by using an STM tip. Strikingly, we demonstrate that the pinned vortices move together with these wrinkles even at high magnetic field up to 6 T. Our results provide a universal and effective routine for manipulating wrinkle-pinned vortices and simultaneously measuring the local density of states on the iron-based superconductor surfaces.

Ordered and tunable Majorana-zero-mode lattice in naturally strained LiFeAs.

Majorana zero modes (MZMs) obey non-Abelian statistics and are considered building blocks for constructing topological qubits1,2. Iron-based superconductors with topological bandstructures have emerged as promising hosting materials, because isolated candidate MZMs in the quantum limit have been observed inside the topological vortex cores3-9. However, these materials suffer from issues related to alloying induced disorder, uncontrolled vortex lattices10-13 and a low yield of topological vortices5-8. Here we report the formation of an ordered and tunable MZM lattice in naturally strained stoichiometric LiFeAs by scanning tunnelling microscopy/spectroscopy. We observe biaxial charge density wave (CDW) stripes along the Fe-Fe and As-As directions in the strained regions. The vortices are pinned on the CDW stripes in the As-As direction and form an ordered lattice. We detect that more than 90 per cent of the vortices are topological and possess the characteristics of isolated MZMs at the vortex centre, forming an ordered MZM lattice with the density and the geometry tunable by an external magnetic field. Notably, with decreasing the spacing of neighbouring vortices, the MZMs start to couple with each other. Our findings provide a pathway towards tunable and ordered MZM lattices as a platform for future topological quantum computation.

Anchoring Copper Single Atoms on Porous Boron Nitride Nanofiber to Boost Selective Reduction of Nitroaromatics.

Single-atom catalysts have received widespread attention for their fascinating performance in terms of metal atom efficiency as well as their special catalysis mechanisms compared to conventional catalysts. Here, we prepared a high-performance catalyst of single-Cu-atom-decorated boron nitride nanofibers (BNNF-Cu) via a facile calcination method. The as-prepared catalyst shows high catalytic activity and good stability for converting different nitro compounds into their corresponding amines both with and without photoexcitation. By combined studies of synchrotron radiation analysis, high-resolution high-angle annular dark-field transmission electron microscopy studies, and DFT calculations, dispersion and coordination of Cu atoms as well as their catalytic mechanisms are explored. The BNNF-Cu catalyst is found to have a record high turnover frequency compared to previously reported non-precious-metal-based catalysts. While the performance of the BNNF-Cu catalyst is only of the middle range level among the state-of-the-art precious-metal-based catalysts, due to the much lower cost of the BNNF-Cu catalyst, its cost efficiency is the highest among these catalysts. This work provides a choice of support material that can promote the development of single-atom catalysts.

A Superlattice-Stabilized Layered CuS Anode for High-Performance Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc ion batteries (AZIBs) are attracting extensive attention owing to environmental friendliness and high safety. However, its practical applications are limited to the poor Coulombic efficiency and stability of a Zn anode. Herein, we demonstrate a periodically stacked CuS-CTAB superlattice, as a competitive conversion-type anode for AZIBs with greatly improved specific capacity, rate performance, and stability. The CuS layers react with Zn2+ to endow high capacity, while CTAB layers serve to stabilize the structure and facilitate Zn2+ diffusion kinetics. Accordingly, CuS-CTAB shows superior rate performance (225.3 mA h g-1 at 0.1 A g-1 with 144.4 mA h g-1 at 10 A g-1) and a respectable cyclability of 87.6% capacity retention over 3400 cycles at 10 A g-1. In view of the outstanding electrochemical properties, full batteries constructed with a CuS-CTAB anode and cathode (ZnxFeCo(CN)6 and ZnxMnO2) are evaluated in coin cells, which demonstrate impressive full-battery performance.

In Situ Studies of 30% Li-Doped Bi25FeO40 Conversion Type Lithium Battery Electrodes.

One of the important discharge mechanisms for lithium batteries is the conversion reaction mechanism, where a metal oxide (fluoride) can decompose into metallic nanoparticles embedded in a Li2O (LiF) matrix. Here, 30% Li-doped Bi25FeO40 is successfully synthesized and displays an electrochemical discharge capacity of ∼300 mAh/g above 1.5 V (vs Li/Li+). During the electrochemical cycling process, 30% Li-doped Bi25FeO40 is decomposed into metallic Bi. During the subsequent charging process, the metallic bismuth can be first converted into an amorphous bismuth oxide phase, which contributed to the electrochemical discharge activities observed between 2 and 2.5 V. At a higher charging voltage between 3.5 and 5 V, metallic Bi can be oxidized to BiO x 2-O3-2x -, which contributes to the discharge activities observed above 2.5 V. Using graphite as current collectors can prevent the corrosion from O- species and the discharge capacity is greatly enhanced at the voltage region between 1.5 and 2.5 V. This work provides a deeper understanding over the role of oxygen ions during the conversion reaction process and is beneficial for the future design of battery systems based on the conversion reaction.

Effect of Tensile Strength on the Microstructure of Graphite Impregnated with Salt Revealed by In Situ Synchrotron-Based Two-Dimensional X-ray Diffraction.

Owing to the inhomogeneous distribution of FLiNaK salt impregnated into graphite which is observed by scanning electron microscopy and an element probe micro-analyzer, a map scan of in situ real-time tensile synchrotron-based two-dimensional X-ray diffraction (2D-XRD) at several fixed external forces was implemented to reveal the local microstructure evolution of graphite and FLiNaK salt. Notably, a stress concentration area (SCA), that is, the main interaction area between graphite and salt, was found and then transformed from one region to another region because of the unbalanced squeeze interaction between graphite and FLiNaK salt with the increase of external force. During the external stress load process, a smaller grain size, poorer crystallinity of graphite and a larger grain size, better crystallinity of FLiNaK salt appear in the SCA; meanwhile, the changes of crystallographic preferred orientation of FLiNaK salt domains in SCA imply that the external load force makes better the ordered stacking of the larger crystal grains of the FLiNaK salt impregnated into graphite. Most importantly, we have found for the first time that the fracture position of graphite impregnated with FLiNaK salt always occurs near the SCA rather than at a fixed region under the external stress load. Thus, the present study not only helps to reveal the interaction mechanism between graphite and FLiNaK salt under the external stress load but also contributes to accurately predict and analyze the stress state of components, which would have an effective impact on the design of a molten salt reactor and the reliability of the component safety assessment.

Iron Vacancies Induced Bifunctionality in Ultrathin Feroxyhyte Nanosheets for Overall Water Splitting.

Exploring of new catalyst activation principle holds a key to unlock catalytic powers of cheap and earth-abundant materials for large-scale applications. In this regard, the vacancy defects have been proven to be effective to initiate catalytic active sites and endow high electrocatalytic activities. However, such electrocatalytically active defects reported to date have been mostly formed by anion vacancies. Herein, it is demonstrated for the first time that iron cation vacancies induce superb water splitting bifunctionality in alkaline media. A simple wet-chemistry method is developed to grow ultrathin feroxyhyte (δ-FeOOH) nanosheets with rich Fe vacancies on Ni foam substrate. The theoretical and experimental results confirm that, in contrast to anion vacancies, the formation of rich second neighboring Fe to Fe vacancies in δ-FeOOH nanosheets can create catalytic active centers for both hydrogen and oxygen evolution reactions. The atomic level insight into the new catalyst activation principle based on metal vacancies is adaptable for developing other transition metal electrocatalysts, including Fe-based ones.

Formation of nano-sized M2C carbides in Si-free GH3535 alloy.

GH3535 alloy is one of the most promising structural materials for molten salt reactors (MSRs). Its microstructure is characterized by equiaxed grains and coarser primary M6C carbide strings. In this study, stable nano-sized M2C carbides were obtained in GH3535 alloy by the removal of Si and thermal exposure at 650 °C. Nano-sized M2C carbide particles precipitate preferentially at grain boundaries during the initial stage of thermal exposure and then spread all over the grain interior in two forms, namely, arrays along the {1 1 1} planes and randomly distributed particles. The precipitate-free zones (PFZs) and the precipitate-enriched zones (PEZs) of the M2C carbides were found to coexist in the vicinity of the grain boundaries. All M2C carbides possess one certain orientation relationship (OR) with the matrix. Based on microstructural characterizations, the formation process of M2C carbides with different morphologies was discussed. The results suggested that the more-stable morphology and OR of M2C carbides in the Si-free alloy provide higher hardness and better post-irradiation properties, as reported previously. Our results indicate the preferential application of Si-free GH3535 alloy for the low-temperature components in MSRs.

High temperature in-situ synchrotron-based XRD study on the crystal structure evolution of C/C composite impregnated by FLiNaK molten salt.

An in-situ real-time synchrotron-based grazing incidence X-ray diffraction was systematically used to investigate the crystal structural evolution of carbon fiber reinforced carbon matrix (C/C) composite impregnated with FLiNaK molten salt during the heat-treatment process. It was found that the crystallographic thermal expansion and contraction rate of interlayer spacing d 002 in C/C composite with FLiNaK salt impregnation is smaller than that in the virgin sample, indicating the suppression on interlayer spacing from FLiNaK salt impregnated. Meanwhile the crystallite size L C002 of C/C composite with FLiNaK salt impregnation is larger than the virgin one after whole heat treatment process, indicating that FLiNaK salt impregnation could facilitate the crystallization of C/C composite after heat treatment process. This improved crystallization in C/C composite with FLiNaK salt impregnation suggests the synthetic action of the salt squeeze effect on crooked carbon layer and the release of internal residual stress after heating-cooling process. Thus, the present study not only contribute to reveal the interaction mechanism between C/C composite and FLiNaK salt in high temperature environment, but also promote the design of safer and more reliable C/C composite materials for the next generation molten salt reactor.

The Effect of Milling Time on the Microstructural Characteristics and Strengthening Mechanisms of NiMo-SiC Alloys Prepared via Powder Metallurgy.

A new generation of alloys, which rely on a combination of various strengthening mechanisms, has been developed for application in molten salt nuclear reactors. In the current study, a battery of dispersion and precipitation-strengthened (DPS) NiMo-based alloys containing varying amounts of SiC (0.5-2.5 wt %) were prepared from Ni-Mo-SiC powder mixture via a mechanical alloying (MA) route followed by spark plasma sintering (SPS) and rapid cooling. Neutron Powder Diffraction (NPD), Electron Back Scattering Diffraction (EBSD), and Transmission Electron Microscopy (TEM) were employed in the characterization of the microstructural properties of these in-house prepared NiMo-SiC DPS alloys. The study showed that uniformly-dispersed SiC particles provide dispersion strengthening, the precipitation of nano-scale Ni3Si particles provides precipitation strengthening, and the solid-solution of Mo in the Ni matrix provides solid-solution strengthening. It was further shown that the milling time has significant effects on the microstructural characteristics of these alloys. Increased milling time seems to limit the grain growth of the NiMo matrix by producing well-dispersed Mo2C particles during sintering. The amount of grain boundaries greatly increases the Hall-Petch strengthening, resulting in significantly higher strength in the case of 48-h-milled NiMo-SiC DPS alloys compared with the 8-h-milled alloys. However, it was also shown that the total elongation is considerably reduced in the 48-h-milled NiMo-SiC DPS alloy due to high porosity. The porosity is a result of cold welding of the powder mixture during the extended milling process.

Carbides Evolution in a Ni-16Mo-7Cr Base Superalloy during Long-Term Thermal Exposure.

The effect of long-term thermal exposure on the carbide evolution in a Ni-16Mo-7Cr base superalloy was investigated. The results show that M12C carbides are mainly precipitated on the grain boundaries during thermal exposure, and the primary massive M6C carbides can be completely transformed to M12C carbides in situ at temperatures above 750 °C for long-term thermal exposure. The transformation from M6C carbides to M12C carbides is attributed to the release of C atoms from M6C, which results in the morphology changes of massive carbides, and stabilization of the sizes of M12C carbides precipitated on the grain boundaries.

TEM investigation on the microstructural evolution of Hastelloy N induced by Ar⁺ ion irradiation.

Hastelloy N alloy has been selected as the primary structure material for molten salt reactor. In this article, Hastelloy N alloy samples were irradiated to different doses at room temperature using 300 keV Ar(+) ions. The microstructural evolution was investigated by transmission electron microscopy (TEM) and energy-dispersive spectroscopy (EDS). Black dot defects emerged in sample irradiated at low dose (0.4 displacement per atom (dpa)), and they grew up with irradiation doses (0.4-2 dpa). A high density of small dislocation loops (nano meters in size) were observed in the sample irradiated to 4 dpa. When the ion dose increased to 12 dpa, complicated structures with defects (including dislocation lines, larger loops and smaller black dots) were observed. Dislocation networks were detected from high-angle annular dark field (HAADF) images. Larger dislocation loops (size: 30-80 nm) were visible in the sample irradiated to 40 dpa. Irradiation with dose of 120 dpa led to the formation of face-centered cubic nanocrystallites with preferred orientations.

Interaction between nuclear graphite and molten fluoride salts: a synchrotron radiation study of the substitution of graphitic hydrogen by fluoride ion.

The interaction between nuclear graphite and molten fluoride salts (46.5 mol % LiF/11.5 mol % NaF/42 mol % KF) is investigated by synchrotron X-ray diffraction and C K-edge X-ray absorption near-edge structure (XANES). It is found that there are a large number of H atoms in IG-110 nuclear graphite, which is attributed to the residual C-H bond after the graphitization process of petroleum coke and pitch binder. The elastic recoil detection analysis indicates that H atoms are uniformly distributed in IG-110 nuclear graphite, in excellent agreement with the XANES results. The XANES results indicate that the immersion in molten fluoride salts at 500 °C led to H atoms in nuclear graphite partly substituted by the fluorine from fluoride salts to form C-F bond. The implications of these findings are discussed.

Facile solid-phase synthesis of the diammoniate of diborane and its thermal decomposition behavior.

The recent mechanistic finding of the hydrogen release pathways from ammonia borane (AB) has sparked new interest in the chemistry and properties of the diammoniate of diborane (DADB), an ionic isomer of AB. We herein report a facile one-step solid-phase synthesis route of DADB using inexpensive starting materials. Our study found that mechanically milling a 1 : 1 NaBH(4)/NH(4)F powder mixture causes the formation of crystalline DADB via a NH(4)BH(4) intermediate. The produced DADB can be readily separated from the sodium fluoride (NaF) by-product by a purification procedure using liquid ammonia at -78 °C. The thermal decomposition behavior of DADB was studied using synchronous thermal analyses, particularly in comparison with AB. It was found that the decomposition steps and products of DADB are similar to those of AB. But meanwhile, DADB exhibits a series of advantages over AB that merit its potential hydrogen storage application, such as lower dehydrogenation temperature, free of foaming and lack of an induction period in the thermal decomposition process. Our study further found that the volatile non-hydrogen products from DADB can be effectively suppressed by milling with MgH(2).

Cubic phase content and structure of BN films from an X-ray absorption study.

X-ray absorption near-edge structure (XANES) was used to study the cubic boron nitride (c-BN) content in the BN films deposited on various substrates by different physical vapor deposition or plasma-enhanced chemical vapor deposition methods. By fitting the XANES curves of thin-film samples using standard spectra of pure c-BN and sp(2)-bonded BN in the films with suitable weight factors, the c-BN contents at the film's surface region and across the film's thickness have been determined quantitatively. The results agree well with the previous transmission electron microscopic observations. The method is proved to be independent of the optical properties of thin film and provides a possibility to evaluate the cubic content of BN films accurately.

Organosulfur-functionalized Au, Pd, and Au-Pd nanoparticles on 1D silicon nanowire substrates: preparation and XAFS studies.

A hybrid preparative method was developed to prepare organosulfur-functionalized Au nanoparticles (NPs) on silicon nanowires (SiNWs) by reacting HAuCl(4) with SiNW in the presence of thiol. A number of organosulfur molecules-dodecanethiol, hexanethiol, 1,6-hexanedithiol, and tiopronin-were used to functionalize the Au surface. Size-selected NPs ranging from 1.6 to 7.5 nm were obtained by varying the S/Au ratio and the concentration of HAuCl(4). This method was further extended to the preparation Pd and Pd-Au bimetallic NPs on SiNWs. The morphology of the metal nanostructures was examined by transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The local structure and bonding of the SiNW-supported metal nanostructures were studied using X-ray absorption fine structures (XAFS) [including both X-ray near-edge structures (XANES) and extended X-ray absorption fine structures (EXAFS)] at the Au L(3)-, Pd K-, S K-, and Si K-edges. It was also found that the annealing of the thiol-capped Au NPs up to 500 degrees C transforms the surface of the thiol-capped NPs to gold sulfide, as identified using Au L(3)- and S K-edge XANES. We also illustrate that this preparative approach can be used to form size-controllable Au NPs on carbon nanotubes.